GB2164898A - Thin polyethylene films - Google Patents

Abstract

Smooth, glossy, thin films based on linear polyethylene with Mw > 4 X 10<5>, preferably above 8 x 10<5>, having a strength above 1 GPa, a modulus above 20 GPa, and a FEM value above 150 KJ/m, and having a thickness of below 25 mu m, preferably below 2 mu m, an opacity below 15% and a water vapour transmission value below 0.6. Such films can be prepared by spinning or extruding a semidiluted solution of polyethylene, thermoreversible gelation of the spun or extruded article, followed by high, biaxial stretching.

Description

1 GB 2 164 898A 1

SPECIFICATION

Thin films of high-molecular polyethylene and process for their preparation The invention relates to films of low thickness with a high tensile strength and a high modulus on the basis of high-molecular polyethylene, and to a process for preparing such films.

It is known how to prepare polyethylene filaments having very high tensile strengths, for instance above 1.2 GPa, and moduli, for instance more than 20 GPa, on the basis of dilute solutions of a high-molecular linear polyethylene, see for instance US-A-4,344,908, US-A-4,422,993 and US-A-4,430,383. In these known processes a solution of at most 50 % (wt), specifically 1-5 % (wt), polyethy]- ene with a weight-average molecular weight of at least 4 X 105, specifically at least 8 X 105, is spun through a spinning aperture at a temperature above the gelling temperature of the solution to form a filament, which is subse- quently cooled to below the gelling temperature, upon which the gel] filament formed in this process is stretched at elevated temperature, whether or not after removal of all or part of the solvent.

It is known also in such processes how to use spinning heads with slitshaped dies instead of spinning heads with virtually round dies, producing tapes instead of round filaments, see for instance US-A-4,411, 854 and US-A-4,436,689.

In the applicant's non-prepu bl i shed Netherlands patent application 8. 402.964 a process is described for preparing polymer films with a high tensile strength and modulus on the basis of dilute solutions of high-molecular polymers via thermoreversible gelling followed by uniaxial stretching.

Although in these processes products are obtained having excellent mechanical proper- ties, these processes are suitable almost exclusively for preparing relatively narrow products, the width of the product being determined by the width of, for instance, the spinning aperture, the opening in the extruder or the flow width of the intermediate gel product on a cooling roll. The preparation of very wide films is therefore not possible in these processes. Also, the preparation of ultra-thin films is virtually ruled out according to the said processes.

From EP-A-1 15.192 it is known how to prepare films, among other things, by dissolving a high-molecular polyethylene at elevated temperature in a paraffin wax which is solid at room temperature, extruding the solution and cooling and successively uniaxially stretching the extrudate. The disadvantage of that process is that a non-smooth product having a very high creep, and moreover, a high degree of opacity and porosity is obtained. Also the FEM value is relatively low (<l50 KJ/m). In this application there is furthermore stated, without giving further particulars, that it is also possible to prepare biaxially stretched films by applying the said process.

The present invention now provides for very wide films of a high strength and modulus with extremely low thickness, on the basis of solutions of high-molecular polyethylene, which do not or hardly show the above disadvantages, and a process for preparing such films.

The present invention in one aspect thereof provides smooth, glossy films based on linear polyethylene with a weight-average molecular weight of at least 4X 105, the film having a tensile strength of at least 1 GPa, a modulus of at least 20 GPa, a FEM value as hereinafter defined, of at least 150 KJ/m, a thickness of at most 25pm, an opacity of at most 15 % and a water vapour transmission value, measured as hereinafter specified, of at most 0.6.

Particularly the invention relates to films wherein the weight-average molecular weight of the linear polyethylene amounts to at least 5 X 105, preferably at least 8 X 105, the tensile strength to at least 1.5 GPa, the modulus to at least 40 GPa, the thickness to at most 5pm, preferably to at most 2pm, the FEM value to at least 200 KJ/m, the opacity to at most 10 %, and the water vapour transmission value to at most 0.5.

The invention further relates to a process for preparing polyethylene film, wherein a solution of a linear polyethylene with a weight- average molecular weight of at least 4X 101 and with at least 50 % (wt) of a solvent, which is liquid at room temperature, is transformed at elevated temperature into a solventcontaining article, this article is converted by rapid cooling to below the gelling temperature into a gel article and this gel article is subjected at a temperature above 75' to biaxial stretching, whether or not after removal of all or part of the solvent, with a stretch ratio lengthwise and breadthwise of at least 3.

Biaxial stretching of polymers in the semisolid phase is known in itself, for instance of polypropylene or polyvinylchloride, see inter alia 'Extrudierte Feinfolien und Verbundfolien' (1976) and 'Folien, Gewebe, Wesstoffen aus Polypropulen' (1979) published by VD1-Verlag G.m.b.H. (Dusseldorf).

It is also known how to subject melted polyethylene to biaxial stretching, see for instance Journal of Applied Polymer Science, Vol. 29 (1984) pages 2347-2357.

In these known processes, however, it is not possible to prepare very thin to ultra-thin films with very high tensile strengths and mo- duli. Moreover, the products obtained via stretching in the semi-solid phase have been found to be relatively brittle.

The essence of a process according to the present invention is that a polyethylene gel article obtained via thermoreversible gelling is 2 GB2164898A 2 subsequently subjected to biaxial stretching.

By means of the process smooth, glossy, wide, extremely thin films having high strength, high toughness, high FEM-value, low opacity, and low porosity (expressed as water 70 vapour transmission) can be obtained.

The tensile strength and modulus of the final film are influenced by the molecular weight of the polymer and the stretch ratio, also by the concentration of the solution.

These parameters can easily be chosen to achieve desirably high tensile strength and modulus values.

The porosity of the final film is dependent or largely dependent on the nature of the sol vent used for forming the polymer solution, and also by the stretch ratio. For achieving low porosity values, the solvent should be one which is easily removable from the gel.

Decalin is one example of such a solvent. Pa raffin waxes are not recommended if low po rosity is a requirement. The porosity tends to increase if very high stretch ratios are reached.

The process enables films with surprisingly 90 low opacity to be formed, e.g. an opacity of 15% or less as above referred to.

Particular importance is attached to pro cesses performed so as to obtain a film hav- ing properties, e.g. a tensile strength, modulus 95 and thickness, specified in claim 1 or 3 hereof.

In the present process a high-molecular lin ear polyethylene with a weight-average mole cular weight of at least 4X 105, particularly at least 5 X 105 and preferably at least 8 X 101, is started from. High-molecular linear polyethyl ene is here understood to include ethylene homopolymer and polymer containing a minor amount, preferably at most 5 moles %, of one or more other alkenes copolymerized with ethylene, such as propylene, butylene, pen tene, hexene, 4-methylpentene, octene, etc.; the polymer in any case having fewer than 1 side chain per 100 carbon atoms, and prefera bly fewer than 1 side chain per 300 carbon atoms. The term---highmolecular weight poly ethylene- moreover includes a polymer mix ture containing in addition to the polyethylene a minor amount, preferably at most 25 % (wt), of one or more other polymers, in parti cular an alkene+polymer such as polypropyl ene, polybutylene or a copolymer of propylene with a minor amount of ethylene.

The polyethylene may contain substantial amounts of fillers. It may also be an advantage to use a polyethylene whose weight average/number-average molecular weight ratio is lower than 5.

As the viscosity of the solution increases when the molecular weight of the polyethylene increases, so that it will be more difficult to process, generally no polyethylene with molecular weights higher than 15 X 106 will be used, although indeed the prersent process is feasible with higher molecular weights. The weight-average molecular weights can be determined according to known methods by gel permeation chromatography and light scattering.

The concentration of the polyethylene in the solution may vary, depending in part on the nature of the solvent and the molecular weight of the polyethylene and the applied method of transformation into an article'.

Solutions with a concentration of more than 40 % (wt) are rather difficult to deal withparticularly when using polyethylene with a very high molecular weight, for instance higher than 1 X 1 0c---on account of the high viscosity that occurs. On the other side, the use of solutions with a concentration of, for instance, less than 0.5 % (wt) has the disadvantage of a loss of yield and an increase in the costs of separating off and recovering solvent.

If the solution is to be transformed via spinning at elevated temperature, a polyethylene solution with a concentration between 2 and 20 % (wt), preferably 2-15 % (wt), will generally be started from.

If the solution is to be transformed via a profiled outlet of a kneader, for instance an extruder, in which this solution has been formed, higher concentrations can in principle be applied; preferably 1-50 % (wt), e.g. 5-25 % (wt).

The choice of the solvent is not critical. Any suitable solvent can be used, such as halogenated or non-halogenated hydrocarbons. In most solvents the polyethylene can be dissolved only at temperatures of at least 90 'C. If the solution is to be transformed via spinning, this will generally be effected in a space under atmospheric pressure. Low- boiling sol- vents will then be less desirable, because they may evaporate from the articles so rapidly that they will act more or less as foaming agents and interfere with the structure thereof.

The transformation of the solution into a film-shaped or ribbon-shaped article can be carried out in various ways, e.g. spinning via a spinning head having a very wide slit die. Of course, instead of being spun the solution can also be poured out on for instance a belt or roll, be extruded, rolled out or calendered.

Another possibility is to add a finely divided high-molecular polyethylene and a solvent for this polyethylene in a weight ratio between 1: 100 and 1: 1, or a prepared suspension, to one end of a long kneader provided with one or more rotary screws, to subject the suspension mixture in it at elevated temperature for 0.5-30 minutes at a high throughput rate to mixing and kneading at high mechani- cal shear rates and to carry off the resulting mixture via an opening at the other end of the kneader into a gaseous or liquid cooling medium or onto a solid cooling surface while a highly stretchable gel article is being formed.

Under rapid cooling solutions of polyethyl- 3 GB2164898A 3 ene materials will change into a gel below a critical temperature (gel point). In for instance spinning a solution must be used and the temperature must therefore be above this gel po5 int.

During for instance the spinning the temperature of the solution is preferably at least 100 'C and more specifically at least 120 'C and the boiling point of the solvent is preferably at least 100 OC and specifically at least equal to the transformation or spinning temperature. The solvent must not have a boiling point so high as to make it difficult for it to be evaporated from the films or ribbons obtained, and must be liquid at room temperature. Suitable solvents are aliphatic, cycloaliphatic and aromatic hydrocarbons with boiling points of at least 100 'C, such as paraffins, toluene, xylenes, tetralin, decalin, Cl-C12alkenes or pe- troleum fractions, but also halogenated hydrocarbons, for instance monochlorobenzene, and other known solvents. On account of the low cost preference will mostly be given to nonsubstituted hydrocarbons, which also include hydrogenated derivatives of aromatic hydrocarbons.

The transformation temperature and the dissolution temperature must not be so high that substantial thermal decomposition of the poly- ethylene occurs. These temperatures will therefore generally not be chosen higher than 240 OC.

The ribbon-shaped or film-shaped product obtained is cooled to below the gel point of the solution. This can be done in any suitable manner, for instance by passing the product into a liquid bath or through a shaft or by pouring it out on a cooling roll. During the cooling to below the gel point of the poly- ethylene solution the polyethylene forms a gel. A film or tape consisting of this polyethylene gel has enough mechanical strength to be processed further, for instance via guides, rolls and the like customary in the spinning tech- nique.

The gel thus obtained is subsequently stretched. In this stretching operation the gel may still contain substantial amounts of solvent, up to amounts hardly lower than those present in the polyethylene solution. Or, be- fore the stretching, part or indeed essentially all of the solvent may be removed from the gel, for instance by evaporation or by washing out with an extractant.

Preference is given to stretching the films or tapes at elevated temperature, specifically above 75 'C. In this operation the stretching will preferably be done below the melting po int or dissolution point of the polyethylene be- cause above that temperature the mobility of the macromolecules will soon be so high that the desired orientation cannot be achieved or only to an insufficient degree. The intramolecular development of heat resulting from the stretching of the films or tapes will be taken into account. At high rates of stretching the temperature in the films or tapes may thus show a strong increase and care must be taken not to allow it to come near or, indeed, to exceed the melting point.

The films or tapes can be brought to the stretching temperature by passing them into a zone containing a gaseous or liquid medium, which zone is kept at the desired temperature.

A tubular oven with air as gaseous medium is very suitable, but a liquid bath or any other appropriate device can be used also.

During the stretching (any) solvent present will be separated off from the film or tape.

This is promoted preferably by appropriate measures, such as carrying off the solvent vapour by passing a hot gas or air stream along the film or tape in the stretching zone, or by stretching in a liquid bath comprising an ex- tractant for the solvent, which extractant may optionally be the same as the solvent. The final film must be free of solvent and it is an advantage for the chosen conditions to be such that this state is reached or substantially so, before and/or during the stretching operation, so that no subsequent treatment, e.g. afterwashing, is required.

Moduli (E) and tensile strength (a) are calculated by means of force/elongation curves as determined at room temperature by means of an Instron Tensile Tester, at a testing speed of 10 % per minute, and reduced to the original cross section of the film sample.

The FEM value is measured via the Instru- mented Flat-Headed Failing-Dart Test, as described in Polymer Testing 2 (1981) pages 69-83. The water vapour transmission value is measured according the standard method mentioned in Kunststoffe/Plastics 7/73, page 25.

In the present process the draw ratios may vary. Generally, the gel will be stretched lengthwise and breadthwise at least 3x and preferably 5 to 25x. In this operation the draw ratio may be the same lengthwise and bread- thwise, or lengthwise a draw ratio may be applied higher than breadthwise. The length wise and breadthwise stretching may be done alternately, but preferably simultaneously.

It may be an advantage for the gel product to be subjected, before or during the stretch ing, to an irradiation, specifically an electron radiation, in which process products are ob tained with reduced creep and fibrillation.

The films according to the invention are suitable for many applications, for instance for packaging film, protective sheeting, substrates for adhesives, as well as for cutting into very thin ribbons or tapes. In view of the extremely low thicknesses of the films that can be pre pared according to the invention, for instance <1 urn, and their low porosity, the films are very suitable to be used as insulating films in condensers.

If so desired, minor amounts of the usual 4 GB2164898A 4 additives, stabilizers, fibre-treating agents and the like can be incorporated in or on the films, specifically amounts of 0.1-10 % (wt) in respect of the polyethylene.

The invention is further elucidated in the following examples without, however, being Hmited by these.

Example 1

A 5 % (wt) solution in decalin of high-molecular linear polyethylene (Hostalen GUR 412 of Ruhrchemieffloechst) with a weight-average molecular weight of about 1.5X1013 was poured out at 175-180 'C through a slitshaped aperture into a cooled box where the film was released of solvent by air being passed along. The non-transparent gel film formed (about 20 em long, 20 em wide and 100 pm thick) was stretched 7x both length- wise and breadthwise at 125 'C to form a film having a length and width of about 140 em and a thickness of about 2 pm.

The thin, smooth and glossy film formed was found to show a strength of 1. 5 GPa and a modulus of 42 GPa. The FEM value was about 200 KJ/m. The tension at break was about 0.2 GPa.

The opacity was about 9 % and the water vapour transmission about 4.5.

(Cf.: The FEM value of LDPE blown film is about 30 KJ/m).

Examples 11-IV The process of example 1 was repeated, but with a 1, 3 and 8 % (wt) solution of Hostalen GUR 412 in decalin.

The results found were virtually the same as those of example 1.

Examples V-011 The process of example 1 was repeated, but with a 1, 3, 5 and 8 % (wt) solution in de calin of a polyethylene grade Hifax-1900 (Her cules) with a weight-average molecular weight of 2 X 106.

The FEM values found were 200-220 KJ/m.

Example IX

The process of example 1 was repeated on the understanding that a gel film 10 em long, em wide and 50 um thick was stretched 10x lengthwise and readthwise at about 130 QC.

The FEM value of the uitra-thin film formed 120 (100 em long, 100 em wide and less than 1 lim thick) was about 240 KJ/m, the strength about 1.6 GPa and the modulus about 45 GPa.

Example X

The process of example 1 was repeated, but this time with a 15 % (wt) solution of Hifax1900 in decalin, obtained in a twin-screw ex- truder of the ZSK type of the firm of Werner and Pfieiderer. The solution was poured out via a slit-shaped aperture in the extruder and further treated as in example 1. The FEM value of the film product formed was 220 KJ/m, the strength about 1,7 GPa, the modulus about 50 GPa and the water vapour transmission about 3.5.

Example Xl

A 5 % (wt) solution of Hostalen GUR 412 in decalin (temp. 180 'C) was poured out via a slit-shaped aperture onto a cooling roll with formation of a film-shaped article of a width of about 60 em. The film was passed through an extraction bath of dichloroethane, upon which the gel film formed (width 60 em, thick ness about 80 pm) was stretched lengthwise about 10x and breadthwise about 8x at about 1250C.

The FEM value of the film formed (about 1 pm thick) was 230 KJ/m. The other values were virtually the same as in Example 1.

CLAWS 1. A smooth, glossy film based on high molecular weight, linear polyethylene, the film being of combined high tensile strength, high modulus, high FEM-value, and low thickness, low opacity and low water vapour transmis- sion value, wherein said weight average molecular weight is at least 4X 105, said tensile strength is at least 1 GPa, said modulus is at least 20 GPa, said FEM value, as herein before defined, is at least 150 KJ/m, said thickness is at most 25 pm, said opacity is at most 15 %, and said water vapour transmission value, mea- sured as herein specified, is at most 0.6. 2. A film according to claim 1, wherein said weight average molecular weight is at least 5 X 105, and said thickness is at most 5 11m.

3. A film according to claim 1 or 2, wherein said weight average molecular weight is at least 8 X 1 W, said tensile strength is at least 1. 5 GPa, said modulus is at least 40 GPa, said FEM value is at least 200 KJ/m, said thickness is at most 2 pm, said opacity is at most 10 %, and said water vapour transmission value is at most 0.5 4. A spun and biaxially stretched film according to any of claims 1-3. 5. A process for preparing polyethylene film which process comprises transforming a solution of a linear polyethylene having an weight-average molecular weight of at least 4 X 105 with at least 50 % (wt) of a solvent which is liquid at room temperature, at elevated temperature into a solvent- containing ar- ticle, converting this article by rapid cooling to below the gelling temperature into a gel article, and subjecting this gel article at a temperature above 75T to biaxial stretching, whether or not after removal of all or part of the solvent, with a stretch ratio lengthwise and breadthwise of at least 3.

6. A process according to claim 5 wherein a 2-20 % (wt) solution of a high-molecular polyethylene is spun at a temperature above the gelling temperature of the solution into a ribbon-shaped or film- shaped article prior to said cooling and biaxial stretching.

7. A process according to claim 5, wherein a 1-50 % (wt) solution of a high-molecular polyethylene obtained in a single or twinscrew extruder is transformed direct, via a slit-shaped die in said extruder, into a ribbonshaped or film-shaped article at a temperature above the gelling temperature of the solution prior to said cooling and biaxial stretching.

8. A process according to any one of claims 5-7, wherein the stretch ratio applied lengthwise is between 5 and 25 and breadthwise between 5 and 25, the stretch ratio lengthwise being equal to or higher than the stretch ratio breadthwise.

9. A process according to any one of claims 5-8, wherein the gel article is stretched lengthwise and breadthwise simulta- neously.

10. A process according to any one of claims 5-9, wheren the gel article, after cool ing, is subjected to irradiation before or during its stretching.

11. A process according to any of claims to 10, performed so that the resulting biaxi ally stretched film has thickness, tensile strength and modulus values as specified in claim 1 or claim 2.

12. A process according to claim 11, per formed so that the resulting biaxially stretched film has the properties specified in claim 1 or 2 hereof.

Printed in the United Kingdom for Her Majesty's Stationery Office, Did 8818935, 1986, 4235. Published at The Patent Office, 25 Southampton Buildings. London, WC2A lAY, from which copies may be obtained.

GB2164898A 5